电催化CO2和硝酸盐还原耦合甘油氧化生成尿素和草酸

doi:10.1016/S1872-2067(24)60085-9

催化学报 ›› 2024, Vol. 63: 270-281.DOI: 10.1016/S1872-2067(24)60085-9

电催化CO₂和硝酸盐还原耦合甘油氧化生成尿素和草酸

周双龙, 石月, 代钰, 詹天荣, 赖建平^*(), 王磊^*()

青岛科技大学化学与分子工程学院, 山东青岛 266042

收稿日期:2024-05-11 接受日期:2024-06-19 出版日期:2024-08-18 发布日期:2024-08-19
通讯作者: *电子信箱: jplai@qust.edu.cn (赖建平),inorchemwl@qust.edu.cn (王磊).
基金资助:
国家自然科学基金(22001143);国家自然科学基金(52072197);山东省高校青年创新与技术基金(2019KJC004);山东杰出青年基金(ZR2019JQ14);泰山学者青年人才计划(tsqn201909114);泰山学者青年人才计划(tsqn201909123);山东自然科学基金(ZR2020YQ34);山东科技创新重大项目(2019 JZZY020405);山东省级自然科学基金重大基础研究项目(ZR2020ZD09)

Continuous-flow electrosynthesis of urea and oxalic acid by CO₂-nitrate reduction and glycerol oxidation

Shuanglong Zhou, Yue Shi, Yu Dai, Tianrong Zhan, Jianping Lai^*(), Lei Wang^*()

Key Laboratory of Eco-Chemical Engineering, Key Laboratory of Optic-electric Sensing and Analytical Chemistry of Life Science, Taishan Scholar Advantage and Characteristic Discipline Team of Eco-Chemical Process and Technology, College of Chemistry and Molecular Engineering, Qingdao University of Science and Technology, Qingdao 266042, Shandong, China

Received:2024-05-11 Accepted:2024-06-19 Online:2024-08-18 Published:2024-08-19
Contact: *E-mail: jplai@qust.edu.cn (J. Lai), inorchemwl@qust.edu.cn (L. Wang).
Supported by:
National Natural Science Foundation of China(22001143);National Natural Science Foundation of China(52072197);Youth Innovation and Technology Foundation of Shandong Higher Education Institutions, China(2019KJC004);Outstanding Youth Foundation of Shandong Province, the China(ZR2019JQ14);Taishan Scholar Young Talent Program(tsqn201909114);Taishan Scholar Young Talent Program(tsqn201909123);Natural Science Foundation of Shandong Province(ZR2020YQ34);Major Scientific and Technological Innovation Project(2019 JZZY020405);Major Basic Research Program of Natural Science Foundation of Shandong Province(ZR2020ZD09)

摘要/Abstract

摘要：

随着全球环境问题日益突出, 寻找可持续的能源和化工生产方式成为迫切需求. CO₂作为一种主要的温室气体, 其再利用和减排成为全球关注的焦点. 同时, 硝酸盐是一种常见的水污染物, 探索有效的处理方式对环境保护至关重要. 利用电催化技术, 一方面可以将CO₂和硝酸根还原生成尿素, 实现对CO₂和硝酸盐的资源化利用; 另一方面, 在另一反应中, 甘油可以被氧化生成草酸. 这两个过程都能直接生产重要的化工产品, 具有重要的经济价值和环保意义. 研究电催化CO₂和硝酸根还原生成尿素的技术, 为可持续能源和化工生产开辟了新的途径. 然而, 在连续流动的电解槽中, 如何高效地实现CO₂和硝酸根还原生成尿素, 同时优化甘油氧化生成草酸的反应条件, 是一个需要克服的挑战.

本文报道了一种简单的水热法一步合成了三金属烯Pd₇₀Cu₁₂Bi₁₈. 高分辨透射电子显微镜和X射线粉末衍射测试结果证明了Pd, Cu和Bi原子均匀地分布在金属烯中. X射线光电子能谱和同步辐射分析结果表明, Pd原子周围电子密度增加, Bi原子周围电子密度降低. 值得注意的是, 具有特殊电子结构的Pd₇₀Cu₁₂Bi₁₈在甘油氧化反应以及CO₂和硝酸根共还原反应中展示出较好的性能. 将Pd₇₀Cu₁₂Bi₁₈应用在配备了9 cm²有效面积的气体扩散电极的连续流动电解槽中, 实现了同时催化阳极区的甘油氧化生成草酸以及阴极区的CO₂和硝酸盐共还原生成尿素. 结果表明, 该电解槽可以在低电池电压(0.9 V)下获得18.7 mA cm^‒2的电流密度, 草酸和尿素在连续流动的电解槽中的法拉第效率分别为67.1%和70.9%. 此外, 稳定性测试结果表明该电解槽经过120小时反应后, 电解槽的电流密度和产物的法拉第效率没有发生衰减. 同位素标记实验结果表明, 生成的尿素来源于CO₂和电解液中的硝酸根. 原位红外测试和理论计算研究表明, *COOH和*NH₂是C‒N键形成的关键中间体. 此外, 对于阴极C‒N键的形成, Pd位点可以为CO₂和NO₃^‒的加氢过程提供质子, Cu位点促进了*COOH的产生, Bi位点可以稳定*COOH. 此外, 对于甘油氧化, 在Pd金属烯中引入Cu和Bi分别促进了甘油中羟基的氧化和C‒C键的断裂.

综上所述, 本文发展了一种双功能金属烯电催化剂, 并实现了在连续流动的电解槽中同时生产尿素和草酸的目标, 为推动绿色环保的电催化技术在化学工业中的应用提供新思路和参考.

关键词: 尿素, 草酸, CO₂, C?N键, 金属烯

Abstract:

Urea and oxalic acid are critical component in various chemical manufacturing industries. However, achieving simultaneous generation of urea and oxalic acid in a continuous-flow electrolyzer is a challenge. Herein, we report a continuous-flow electrolyzer equipped with 9-square centimeter-effective area gas diffusion electrodes (GDE) which can simultaneously catalyze the glycerol oxidation reaction in the anode region and the reduction reaction of CO₂ and nitrate in the cathode region, producing oxalic acid and urea at both the anode and cathode, respectively. The current density at low cell voltage (0.9 V) remained above 18.7 mA cm^-2 for 10 consecutive electrolysis cycles (120 h in total), and the Faraday efficiency of oxalic acid (67.1%) and urea (70.9%) did not decay. Experimental and theoretical studies show that in terms of the formation of C-N bond at the cathode, Pd-sites can provide protons for the hydrogenation process of CO₂ and NO₃^-, Cu-sites can promote the generation of *COOH and Bi-sites can stabilize *COOH. In addition, in terms of glycerol oxidation, the introduction of Cu and Bi into Pd metallene promotes the oxidation of hydroxyl groups and the cleavage of C-C bond in glycerol molecules, respectively.

Key words: Urea, Oxalic acid, CO₂, C-N bond, Metallene

周双龙, 石月, 代钰, 詹天荣, 赖建平, 王磊. 电催化CO₂和硝酸盐还原耦合甘油氧化生成尿素和草酸[J]. 催化学报, 2024, 63: 270-281.

Shuanglong Zhou, Yue Shi, Yu Dai, Tianrong Zhan, Jianping Lai, Lei Wang. Continuous-flow electrosynthesis of urea and oxalic acid by CO₂-nitrate reduction and glycerol oxidation[J]. Chinese Journal of Catalysis, 2024, 63: 270-281.

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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(24)60085-9

https://www.cjcatal.com/CN/Y2024/V63/I8/270

图/表 5

Fig. 1. The synthesis process of catalysts and morphology of Pd70Cu12Bi18 metallene. (a) Low resolution TEM images of catalysts. (b) Test results of atomic force microscope for Pd70Cu12Bi18 metallene. (c) High resolution TEM images of catalysts. (d) Mapping results of catalyst.

Fig. 2. Electronic structure characterization of synthesized catalysts. (a) Comparison of Fine XPS for Pd 3d. (b) Comparison of Fine XPS for Cu 2p. (c) Comparison of Fine XPS for Bi 4f. (d) XANES spectra for Pd K-edge. (e) XANES spectra for Cu K-edge. (f) XANES spectra for Bi LIII-edge.

Fig. 3. Properties of electrocatalytic CNRR. (a) The LSV curves of synthetized catalysts. (b) Faraday efficiency of products in potassium nitrate solutions of different concentrations. (c) Faraday efficiency distribution of urea at different nitrate concentrations and potentials. (d) NMR spectroscopy of ammonia produced by urease driven isotope labeling urea. (e) NMR spectroscopy of isotope labeled urea and products. (f) Comparison of results of three methods for detecting urea. (g) Comparison of recent advanced catalysts.

Fig. 4. Experimental and theoretical research on the reaction mechanism. In situ FTIR spectroscopy of Pd71Cu29 (a), Pd70Bi30 (b) and Pd70Cu12Bi18 (c) metallene. (d) The comparison of the peak integral area of *COOH under different applied potentials. (e) Comparison of Faraday efficiency of urea under different carbon or nitrogen sources. Free energy diagrams of carbon dioxide (f), nitrate (g) and nitrate and carbon dioxide (h) reduction pathways on Pd70Bi30, Pd71Cu29 and Pd70Cu12Bi18 metallene.

Fig. 5. Performance of electrooxidized glycerol and performance of GOR coupled CNRR. (a) CV curves of synthesized catalysts. (b) Comparison of GOR activity of catalysts. (c) Faraday efficiency under different applied potentials. (d) Free energy diagrams of GOR on Pd70Bi30, Pd71Cu29 and Pd70Cu12Bi18 metallene. (e) Flow electrolytic cell model. (f) Faraday efficiency of urea and oxalic acid at different cell voltages. (g) 120 h of stability testing and corresponding Faraday efficiency.

参考文献

[1]	J. Li, Y. Zhang, K. Kuruvinashetti, N. Kornienko, Nat. Rev. Chem., 2022, 6, 303-319.
[2]	D. Zhang, Y. Xue, X. Zheng, C. Zhang, Y. Li, Natl. Sci. Rev., 2023, 10, nwac209.
[3]	X. Peng, L. Zeng, D. Wang, Z. Liu, Y. Li, Z. Li, B. Yang, L. Lei, L. Dai, Y. Hou, Chem. Soc. Rev., 2023, 52, 2193-2237.
[4]	M. Yuan, J. Chen, Y. Xu, R. Liu, T. Zhao, J. Zhang, Z. Ren, Z. Liu, C. Streb, H. He, C. Yang, S. Zhang, G. Zhang, Energy Environ. Sci., 2021, 14, 6605-6615.
[5]	Y. Zhao, Y. Ding, W. Li, C. Liu, Y. Li, Z. Zhao, Y. Shan, F. Li, L. Sun, F. Li,, Nat. Commun., 2023, 14, 4491.
[6]	X. Cao, D. Zhang, Y. Gao, O. V. Prezhdo, L. Xu, J. Am. Chem. Soc., 2024, 146, 1042-1052.
[7]	S. Liu, M. Wang, Q. Cheng, Y. He, J. Ni, J. Liu, C. Yan, T. Qian, ACS Nano, 2022, 16, 17911-17930.
[8]	Y. Mao, Y. Jiang, Q. Gou, S. Lv, Z. Song, Y. Jiang, W. Wang, M. Li, L. Zheng, W. Su, R. He, Appl. Catal. B, 2024, 340, 123189.
[9]	C. Guo, W. Zhou, X. Lan, Y. Wang, T. Li, S. Han, Y. Yu, B. Zhang, J. Am. Chem. Soc., 2022, 144, 16006-16011.
[10]	N. Meng, J. Shao, H. Li, Y. Wang, X. Fu, C. Liu, Y. Yu, B. Zhang, Nat. Commun., 2022, 13, 5452.
[11]	Z. Tao, C. L. Rooney, Y. Liang, H. Wang, J. Am. Chem. Soc., 2021, 143, 19630-19642.
[12]	X. Wei, X. Wen, Y. Liu, C. Chen, C. Xie, D. Wang, M. Qiu, N. He, P. Zhou, W. Chen, J. Cheng, H. Lin, J. Jia, X. Z. Fu, S. Wang, J. Am. Chem. Soc., 2022, 144, 11530-11535.
[13]	R. Miao, D. Chen, Z. Guo, Y. Zhou, C. Chen, S. Wang, Appl. Catal. B, 2024, 344, 123662.
[14]	M. Sun, G. Wu, J. Jiang, Y. Yang, A. Du, L. Dai, X. Mao, Q. Qin, Angew. Chem. Int. Ed., 2023, 62, e202301957.
[15]	Y. Jiao, H. Li, Y. Jiao, S. Z. Qiao, J. Am. Chem. Soc., 2023, 145, 15572-15580.
[16]	J. Geng, S. Ji, M. Jin, C. Zhang, M. Xu, G. Wang, C. Liang, H. Zhang, Angew. Chem. Int. Ed., 2023, 62, e202210958.
[17]	J. Mukherjee, S. Paul, A. Adalder, S. Kapse, R. Thapa, S. Mandal, B. Ghorai, S. Sarkar, U. K. Ghorai, Adv. Funct. Mater., 2022, 32, 2200882.
[18]	M. Jiang, M. Zhu, M. Wang, Y. He, X. Luo, C. Wu, L. Zhang, Z. Jin, ACS Nano, 2023, 17, 3209-3224.
[19]	G.-L. Yang, C.-T. Hsieh, Y.-S. Ho, T.-C. Kuo, Y. Kwon, Q. Lu, M.-J. Cheng, ACS Catal., 2022, 12, 11494-11504.
[20]	Z. Ma, Y. Luo, P. Wu, J. Zhong, C. Ling, Y. Yu, X. Xia, B. Song, L. Ning, Y. Huang, Adv. Funct. Mater., 2023, 33, 2302475.
[21]	M. Yuan, J. Chen, H. Zhang, Q. Li, L. Zhou, C. Yang, R. Liu, Z. Liu, S. Zhang, G. Zhang, Energy Environ. Sci., 2022, 15, 2084-2095.
[22]	J. Leverett, T. Tran‐Phu, J. A. Yuwono, P. Kumar, C. Kim, Q. Zhai, C. Han, J. Qu, J. Cairney, A. N. Simonov, R. K. Hocking, L. Dai, R. Daiyan, R. Amal, Adv. Energy Mater., 2022, 12, 2201500.
[23]	X. Zhu, X. Zhou, Y. Jing, Y. Li, Nat. Commun., 2021, 12, 4080.
[24]	M. Yuan, J. Chen, Y. Bai, Z. Liu, J. Zhang, T. Zhao, Q. Wang, S. Li, H. He, G. Zhang, Angew. Chem. Int. Ed., 2021, 60, 10910-10918.
[25]	X. Zhang, X. Zhu, S. Bo, C. Chen, M. Qiu, X. Wei, N. He, C. Xie, W. Chen, J. Zheng, P. Chen, S. P. Jiang, Y. Li, Q. Liu, S. Wang, Nat. Commun., 2022, 13, 5337.
[26]	S. Zhang, J. Geng, Z. Zhao, M. Jin, W. Li, Y. Ye, K. Li, G. Wang, Y. Zhang, H. Yin, H. Zhang, H. Zhao, EES Catal., 2023, 1, 45-53.
[27]	X. Yu, R. B. Araujo, Z. Qiu, E. Campos dos Santos, A. Anil, A. Cornell, L. G. M. Pettersson, M. Johnsson, Adv. Energy Mater., 2022, 12, 2103750.
[28]	W. Hong, C. Shang, J. Wang, E. Wang, Energy Environ. Sci., 2015, 8, 2910-2915.
[29]	L. Pan, J. Wang, F. Lu, Q. Liu, Y. Gao, Y. Wang, J. Jiang, C. Sun, J. Wang, X. Wang, Angew. Chem. Int. Ed., 2023, 62, e202216835.
[30]	Y. Wang, S. Xia, J. Zhang, Z. Li, R. Cai, C. Yu, Y. Zhang, J. Wu, Y. Wu, ACS Energy Lett., 2023, 8, 3373-3380.
[31]	S. Shin, S. Sultan, Z.-X. Chen, H. Lee, H. Choi, T.-U. Wi, C. Park, T. Kim, C. Lee, J. Jeong, H. Shin, T.-H. Kim, H. Ju, H. C. Yoon, H.-K. Song, H.-W. Lee, M.-J. Cheng, Y. Kwon, Energy Environ. Sci., 2023, 16, 2003-2013.
[32]	X. Liu, Y. Jiao, Y. Zheng, M. Jaroniec, S. Z. Qiao, Nat. Commun., 2022, 13, 5471.
[33]	A. Zalineeva, A. Serov, M. Padilla, U. Martinez, K. Artyushkova, S. Baranton, C. Coutanceau, P. B. Atanassov, J. Am. Chem. Soc., 2014, 136, 3937-3945.
[34]	S. Li, J. Lai, R. Luque, G. Xu, Energy Environ. Sci., 2016, 9, 3097-3102.
[35]	H. Sheng, A. N. Janes, R. D. Ross, H. Hofstetter, K. Lee, J. R. Schmidt, S. Jin, Nat. Catal., 2022, 5, 716-725.
[36]	D. Liu, J. C. Liu, W. Cai, J. Ma, H. B. Yang, H. Xiao, J. Li, Y. Xiong, Y. Huang, B. Liu, Nat. Commun., 2019, 10, 1779.
[37]	L. S. Oh, M. Park, Y. S. Park, Y. Kim, W. Yoon, J. Hwang, E. Lim, J. H. Park, S. M. Choi, M. H. Seo, W. B. Kim, H. J. Kim, Adv. Mater., 2022, 35, 2203285.
[38]	J. Lai, F. Lin, Y. Tang, P. Zhou, Y. Chao, Y. Zhang, S. Guo, Adv. Energy Mater., 2019, 9, 1800684.
[39]	Y. Liu, X. Tu, X. Wei, D. Wang, X. Zhang, W. Chen, C. Chen, S. Wang, Angew. Chem. Int. Ed., 2023, 62, e202300387.
[40]	N. Meng, X. Ma, C. Wang, Y. Wang, R. Yang, J. Shao, Y. Huang, Y. Xu, B. Zhang, Y. Yu, ACS Nano, 2022, 16, 9095-9104.
[41]	C. Lv, J. Liu, C. Lee, Q. Zhu, J. Xu, H. Pan, C. Xue, Q. Yan, ACS Nano, 2022, 16, 15512-15527.
[42]	X. Wei, Y. Liu, X. Zhu, S. Bo, L. Xiao, C. Chen, T. T. T. Nga, Y. He, M. Qiu, C. Xie, D. Wang, Q. Liu, F. Dong, C. L. Dong, X. Z. Fu, S. Wang, Adv. Mater., 2023, 35, 2300020.

电催化CO₂和硝酸盐还原耦合甘油氧化生成尿素和草酸

Continuous-flow electrosynthesis of urea and oxalic acid by CO₂-nitrate reduction and glycerol oxidation

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